Process for the production of polyhydroxy lignin-cellulose silicate polymer

ABSTRACT

An alkali metal broken-down plant silicate polymer is reacted with a Lewis acid and an epoxide compound to produce a polyhydroxy lignin-cellulose polymer which may be reacted with polyisocyanates to produce polyurethane silicate foam and be used for insulation.

CROSS-REFERENCE TO RELATED CO-PENDING APPLICATIONS

This application is a divisional of U.S. patent application, Ser. No.372,298, filed on Apr. 27, 1982, which is a continuation-in-part of U.S.patent application, Ser. No. 306,184, filed on Sept. 28, 1981, now U.S.Pat. No. 4,367,326, which is a continuation-in-part of U.S. patentapplication, Ser. No. 257,126, filed on Apr. 24, 1981, now U.S. Pat. No.4,313,857, which is a continuation-in-part of U.S. patent application,Ser. No. 203,730, filed on Nov. 3, 1980, now U.S. Pat. No. 4,281,110,which is a continuation-in-part of U.S. patent application, Ser. No.112,290, filed on Jan. 15, 1980, now U.S. Pat. No. 4,243,757 which is acontinuation-in-part of my U.S. patent application, Ser. No. 029,202,filed on Apr. 12, 1979, now U.S. Pat. No. 4,220,757.

SUMMARY OF THE INVENTION

This invention relates to the production of polyhydroxy lignin-cellulosesilicate polymer by chemically reacting an alkali metal broken-downplant silicate polymer with a Lewis acid and an epoxide compound.

The process to produce the broken-down alkali metal plant polymer isoutlined in U.S. patent application, Ser. No. 029,202, filed on Apr. 12,1979, by David H. Blount, M.D., now U.S. Pat. No. 4,220,757, which isincorporated into this application.

The polyhydroxy lignin-cellulose silicate polymer may be used to produceuseful resins and foams such as polyurethane resins and foams, polyesterlignin-cellulose resins and foams and polyester amides resins and foamswhich may be used as molding powder, coating agents, thermal- andsound-insulating foams, etc.

The primary object of this invention is to provide a novel process forthe production of a polyhydroxy lignin-cellulose silicate polymer.Another object is to produce a novel polyhydroxy lignin-cellulosesilicate polymer product. Another object is to produce polyhydroxylignin-cellulose silicate polymers which will react with polyisocyanatecompound to produce useful solid and foamed products. Another object isto produce polyhydroxy lignin-cellulose silicate polymers which willreact with polycarboxylic acid and/or polycarboxylic acid anhydrides toproduce useful polyester lignin-cellulose silicate resins.

Polyhydroxy lignin-cellulose polymers are produced by mixing andreacting the following components:

(a) broken-down alkali metal plant silicate polymer;

(b) epoxide compound;

(c) Lewis acid.

Component (a)

The broken-down water-soluble alkali metal plant silicate polymer isproduced by heating a mixture of 3 parts by weight of acellulose-containing plant and 1 to 2 parts by weight of an oxidatedsilicon compound with 2 to 5 parts by weight of a melted alkali metalhydroxide to between 150° C. and 220° C. while agitating for 5 to 60minutes. The broken-down alkali metal lignin cellulose silicate polymeris soluble in water, alcohols, polyols, and other organic solvents andis a thick liquid above 150° C. and a brown solid below 150° C. Thebroken-down alkali metal plant silicate polymer has lost a carbondioxide radical from each molecule and the lignin-cellulose bond appearsto be intact. When a plant product (cellulose) with the lignin removedis used in the production of broken-down alkali metal plant silicatepolymer, a dark-brown-colored, water-soluble polymer is produced.

Any suitable alkali metal hydroxide may be used to produce broken-downalkali metal plant polymers; sodium hydroxide is preferred. Any suitablecellulose-containing plant or plant product may be used to producebroken-down alkali metal plant polymers such as trees, shrubs,agricultural plants, seaweeds, pulp wood, cotton, decomposedcellulose-containing plants such as humus, peat and certain soft browncoal, etc.

Any suitable oxidated silicon compound may be used in this invention.Suitable oxidated silicon compounds include silica, e.g., hydratedsilica, hydrated silica containing Si-H bonds (silicoformic acid),silica sol, silicic acid, silica; alkali metal silicates, e.g., sodiumsilicate, potassium silicate, lithium silicate, etc., natural silicateswith free silicic acid groups and mixtures thereof. Hydrated silica isthe preferred oxidated silicon compound.

Component (b)

Any suitable epoxide compound may be used in this invention. Suitableepoxide compounds include, but are not limited to, alkylene oxides,e.g., ethylene oxide, propylene oxide, butylene oxide; epihalohydrins,e.g., epichlorohydrin, epibromohydrin, methyl epichlorohydrin,di-epi-iodohydrin, epifluorohydrin, epiiodohydrin; substituted butyleneoxide, e.g., trichlorobutylene oxide; tetrahydrofuran, styrene oxide andmixtures thereof.

Component (c)

Any suitable Lewis acid which will react with alkali metal radical toproduce a salt may be used in this invention. A Lewis acid is anyelectron acceptor relative to other reagents present in the system. ALewis acid will tend to accept a pair of electrons furnished by anelectron donor (or Lewis base) in the process of forming a chemicalcompound. A "Lewis acid" is defined for the purpose of this invention asany electron-accepting material relative to the polymer to which it iscomplexed.

Typical Lewis acids are: 2,5-dichlorobenzoquinone;2,6-dichlorobenzoquinone; chloranil; 1-chloroanthraquinone;anthraquinone-2-carboxylic acid; 1,5-dichloroanthraquinone;1-chloro-4-nitroanthraquinone; anthraquinone-1, 8-disulfonic acid andanthraquinone-2-aldehyde; 4-nitrobenzaldehyde;2,6-dichlorobenzaldehyde-2; ethoxy-1-naphthalidehyde; organic phosphonicacids such as 4-chloro-3-nitrobenzene-phosphonic acid nitrophenols;4-nitrophenol; picric acid; acid anhydrides such as, for example,acetic-anhydride, succinic anhydride, maleic anhydride, phthalicanhydride, tetrachlorophthalic anhydride, perylene3,4,9,10-tetracarboxylic acid and chrysene-2,3,8,9-tetracarboxylicanhydride; dibromo maleic acid anhydride; metal halides of the metalsand metalloids of the groups IB, II through to group VIII of theperiodical system, for example: Aluminum chloride, zinc chloride, ferricchloride, tin tetrachloride (stannic chloride), arsenic trichloride,stannous chloride, antimony pentachloride, magnesium chloride, magnesiumbromide, calcium bromide, calcium iodide, strontium bromide, chromicbromide, manganous chloride, cobaltous chloride, cobaltic chloride,cupric bromide, ceric chloride, thorium chloride, arsenic tri-iodide;baron halide compounds, for example; Boron trifluoride, and borontrichloride; acetoacetic acid anilide, and acenaphthenequinone-dichloride.

Additional Lewis acids are mineral acids such as the hydrogen halides,sulphuric acid and phosphoric acid; organic carboxylic acids, such asacetic acid and the substitution products thereof, monochloro-aceticacid, di-chloroacetic acid, trichloro-acetic acid, phenylacetic acid,and 6-methylcoumarinylacetic acid (4); maleic acid; cinnamic acid;benzoic acid; 1-(4-diethyl-amino-benzoyl)-benzene-2-carboxylic acid;phthalic acid; and tetrachlorophthalic acid;alpha-beta-dibromo-beta-formyl-acrylic acid (mucobromic acid);dibromo-maleic acid; 2-bromo-benzoic acid; gallic acid;3-nitro-2-hydroxy-1-benzoic acid; 2-nitro-phenoxy-acetic acid;2-nitro-benzoic acid; 3-nitro-benzoic acid; 4-nitrobenzoic acid;3-nitro-4-ethoxy-benzoic acid; 3-nitro-4-methoxy-benzoic acid;4-nitro-1-methyl-benzoic acid; 2-chloro-5-nitro-1-benzoic acid;3-chloro-6-nitro-1-benzoic acid; 4-chloro-3-nitro-1-benzoic acid;5-chloro-3-nitro-2-hydroxybenzoic acid; 4-chloro-2-hydroxy-benzoic acid;2,4-dinitro-1-benzoic acid; 2-bromo-5-nitro-benzoic acid;4-chlorophenyl-acetic acid, 2-chloro-cinnamic acid; 2-cyano-cinnamicacid; 2,4-dichlorobenzoic acid; 3,5-dinitro-benzoic acid;3,5-dinitro-salycylic acid; malonic acid; mucic acid, acetosalycylicacid; benzilic acid; butane-tetracarboxylic acid; citric acid;cyano-acetic acid; cyclo-hexane-dicarboxylic acid;cyclo-hexane-carboxylic acid; 9,10-dichlorostearic acid; fumaric acid;itaconic acid; levulinic acid (levulic acid); malic acid; succinic acid;alphabromo-stearic acid; citraconic acid; dibromo-succinic acid;pyrene-2,3,7,8-tetra-carboxylic acid; tartaric acid; organic sulphonicacids such as 4-toluene sulphonic acid and benzene sulphonic acid;2,4-dinitro-1-methyl-benzene-6-sulphonic acid;2,6-dinitro-1-hydroxy-benzene-4-sulphonic acid;2-nitro-1-hydroxy-benzene-4-sulphonic acid;4-nitro-1-hydroxy-2-benzene-sulphonic acid;3-nitro-2-methyl-1-hydroxy-benzene-5-sulphonic acid;6-nitro-4-methyl-1-hydroxy-benzene-2-sulphonic acid;4-chloro-1-hydroxy-benzene-3-sulphonic acid;2-chloro-3-nitro-1-methyl-benzene-5-sulphonic acid and2-chloro-1-methyl-benzene-4-sulphonic acid.

DETAILED DESCRIPTION OF THE INVENTION

The preferred process for producing polyhydroxy lignin-cellulosesilicate polymer is to mix 100 parts by weight of broken-down alkalimetal plant silicate polymer with 1 to 300 parts by weight of an epoxidecompound, then slowly add a Lewis acid while agitating until the pH isabout 5 to 6 and keeping the temperature of the mixture below theboiling temperature of the epoxide compound; then the mixture isagitated for 30 minutes to eight hours, thereby producing a polyhydroxylignin-cellulose silicate polymer.

The reactions of this invention may take place under any suitablephysical condition. While most of the reactions will take place atambient pressure, in certain cases, a pressure either lower than, orabove, ambient pressure may give best results. When the epoxide compoundis a gas, elevated pressures are necessary. A pressure wherein theepoxide compound is in a liquid form is preferred.

In an alternate method, the Lewis acid may be added and reacted with thebroken-down alkali metal plant silicate polymer until the pH is about 5to 6 when tested in an aqueous solution; then the epoxide compound isadded and reacted with the lignin-cellulose silicate polymer. Thecomponents may also be added simultaneously.

In another alternate method, an aldehyde compound may be added with thecomponents in an amount of 1 to 100 parts by weight to 100 parts byweight of the broken-down alkali metal plant silicate polymer. Thealdehyde may also be first reacted with the broken-down alkali metalplant silicate polymer before Components (b) and (c) are added.

Any suitable aldehyde compound may be reacted with the broken-downalkali metal plant silicate polymer. Suitable aldehydes include, but arenot limited to, formaldehyde, acetaldehyde, propionic aldehyde,furfural, crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde,pentanals, hexanals, heptanals, and mixtures thereof in the ratio of 1to 100 parts by weight of the aldehyde to 100 parts by weight of thebroken-down alkali metal plant silicate polymers. The aldehyde may bemixed with the water-soluble broken-down alkali metal plant silicatepolymer, then agitated at a temperature between ambient temperature andthe boiling temperature of the aldehyde and at ambient pressure for from10 to 120 minutes, thereby producing an aldehyde alkali metallignin-cellulose silicate polymer.

Any suitable salt-forming compound may be used in this invention toreact with the broken-down alkali metal lignin-cellulose silicatepolymer. Suitable salt-forming compounds include mineral acids such ashydrochloric acid, sulfuric acid and nitric acid, organic acid such asacetic acid, propionic acid, etc., and hydrogen-containing acid saltssuch as sodium hydrogen sulfate, potassium hydrogen sulfate, sodiumdihydrogen phosphate and potassium dihydrogen phosphate, and mixturesthereof.

The polyhydroxy lignin-cellulose silicate polymer will react withpolyisocyanates such as crude MDI to produce resinous products which maybe used as adhesives, putty caulking agents, etc., and foams which maybe used for thermal and sound insulation.

Any suitable organic polyisocyanate may be used according to theinvention, including aliphatic, cycloaliphatic, araliphatic, aromaticand heterocyclic polyisocyanates and mixtures thereof. Suitablepolyisocyanates which may be employed in the process of the inventionare exemplified by the organic diisocyanates which are compounds of thegeneral formula:

    O═C═N--R--N═C═O

wherein R is a divalent organic radical such as an alkylene, aralkyleneor arylene radical. Such suitable radicals may contain, for example, 2to 20 carbon atoms. Examples of such diisocyanates are:

tolylene diisocyanate,

p,p'-diphenylmethane diisocyanate,

phenylene diisocyanate,

m-xylylene diisocyanate,

chlorophenylene diisocyanate,

benzidene diisocyanate,

naphylene diisocyanate,

decamethylene diisocyanate,

hexamethylene diisocyanate,

pentamethylene diisocyanate,

tetramethylene diisocyanate,

thiodipropyl diisocyanate,

propylene diisocyanate, and

ethylene diisocyanate.

Other polyisocyanates, polyisothiocyanates and their derivatives may beequally employed. Fatty diisocyanates are also suitable and have thegeneral formula: ##STR1## where x+y totals 6 to 22 and z is 0 to 2,e.g., isocyanastearyl isocyanate.

It is generally preferred to use commercially readily-availablepolyisocyanates, e.g., tolylene-2,4- and -2,6-diisocyanate and anymixtures of these isomers, commercially known as "TDI";polyphenylpolymethylene-isocyanates obtained by aniline-formaldehydecondensation followed by phosgenation, commercially known as "MDI"; andmodified polyisocyanate containing carbodiimide groups, allophanategroups, isocyanurate groups, urea groups, imide groups, amide groups orbiuret groups, said modified polyisocyanates prepared by modifyingorganic polyisocyanates thermally or catalytically by air, water,urethanes, alcohols, amides, amines, carboxylic acids, or carboxylicacid anhydrides, phosgenation products of condensates or aniline oranilines alkyl-substituted on the nucleus with formaldehydes or ketonesmay be used in this invention. Solutions of distillation residuesaccumulating during the production of tolylene diisocyanates, diphenylmethane diisocyanates, or hexamethylene diisocyanate, in monomericpolyisocyanates or in organic solvents, or mixtures thereof may be usedin this invention. Organic triisocyanates such as triphenylmethanetriisocyanate may be used in this invention. Cycloaliphaticpolyisocyanates, e.g., cyclohexylene-1,2-; cyclohexylene-1,4-; andmethylene-bis-(cyclohexyl-4,4'-) diisocyanate may be used in thisinvention. Suitable polyisocyanates which may be used according to theinvention are described by W. Siefkin in Justus Liebigs Annalen derChemie, 562, pages 75 to 136. Inorganic polyisocyanates are alsosuitable according to the invention.

Organic polyhydroxyl compounds (polyols) may be used in this inventionwith polyisocyanates or may be first reacted with a polyisocyanate toproduce isocyanate-terminated polyurethane prepolymers and then also beused in this invention.

Reaction products of from 50 to 99 mols of aromatic diisocyanates withfrom 1 to 50 mols of conventional organic compounds with a molecularweight or, generally, from about 200 to about 10,000 which contain atleast two hydrogen atoms capable of reacting with isocyanates, may alsobe used. While compounds which contain amino groups, thiol groups,carboxyl groups or silicate groups may be used, it is preferred to useorganic polyhydroxyl compounds, in particular, compounds which containfrom 2 to 8 hydroxyl groups, especially those with a molecular weight offrom 800 to about 10,000 and, preferably, from about 1,000 to about6,000, e.g., polyesters, polyethers, polythioethers, polyacetals,polycarbonates or polyester amides containing at least 2, generally from2 to 8, but, preferably, dihydric alcohols, with the optional additionof trihydric alcohols, and polybasic, preferably dibasic, carboxylicacids. Instead of the free polycarboxylic acids, the correspondingpolycarboxylic acid anhydrides or corresponding polycarboxylic acidesters of lower alcohols or their mixtures may be used for preparing thepolyesters. The polycarboxylic acid may be aliphatic, cycloaliphatic,aromatic and/or heterocyclic and may be substituted, e.g., with halogenatoms and may be unsaturated. Examples include: Succinic acid, adipicacid, sebacic acid, suberic acid, azelaic acid, phthalic acid, phthalicacid anhydride, isophthalic acid, tetrahydrophthalic acid anhydride,trimellitic acid, hexahydrophthalic acid anhydride, tetrachlorophthalicacid anhydride, endomethylene tetrahydrophthalic acid anhydride,glutaric acid anhydride, fumaric acid, maleic acid, maleic acidanhydride, dimeric and trimeric fatty acid such as oleic acid,optionally mixed with monomeric fatty acids, dimethylterephthalate andbis-glycol terephthalate. Any suitable polyhydric alcohol may be used,such as, for example, ethylene glycol, propylene-1,2- and -1,3-glycol;butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol;neopentyl glycol;cyclohexanedimethanol-(1,4-bis-hydroxymethylcyclohexane);2-methylpropane-1,3-diol; glycerol; trimethylol propane;hexane-1,2,6-triol; butane-1,2,4-triol; trimethylol ethane;pentaerythritol; quinitol; mannitol and sorbitol; methylglycoside;diethylene glycol; triethylene glycol; tetra ethylene glycol;polyethylene glycols; dipropylene glycol; polypropylene glycols;dibutylene glycol and polybutylene glycols. The polyesters may alsocontain a proportion of carboxyl end groups. Polyesters of lactones suchas c-caprolactone, or hydroxycarboxylic acid such as c-hydroxycaproicacid may also be used.

The polyethers with at least 2, generally from 2 to 8 and, preferably, 2to 3, hydroxyl groups used according to the invention are known and maybe prepared, e.g., by the polymerization of epoxides, e.g., ethyleneoxide, propylene oxide, butylene oxide, tetrahydrofurane oxide, styreneoxide or epichlorohydrin, each with itself, e.g., in the presence of BF₃or by addition of these epoxides, optionally as mixtures orsuccessively, to starting components which contain reactive hydrogenatoms such as alcohols or amines, e.g., water, ethylene glycol;propylene-1,3- or -1,2-glycol; trimethylol propane;4,4-dihydroxydiphenylpropane; aniline; ammonia, ethanolamine orethylenediamine; sucrose polyethers, such as those described in GermanAuslegeschrifren Nos. 1,176,358 and 1,064,938, may also be usedaccording to the invention. It is frequently preferred to use polyetherswhich contain, predominantly, primarily OH groups (up to 90% by weight,based on the total OH groups contained in the polyether). Polyethersmodified with vinyl polymers such as those which may be obtained bypolymerizing styrene or acrylonitriles in the presence of polyethers,(U.S. Pat. Nos. 3,383,351; 3,304,273; 3,523,093 and 3,100,695; andGerman Patent No. 1,152,536) and polybutadienes which contain OH groupsare also suitable.

By "polythioethers" are meant, in particular, the condensation productsof thiodiglycol with itself and/or with other glycols, dicarboxylicacids, formaldehyde, aminocarboxylic acids or amino alcohols. Theproducts obtained are polythiomixed ethers or polythioethers esteramides, depending on the component.

The polyacetals used may be, for example, the compounds which may beobtained from glycols, 4,4'-dihydroxydiphenylmethylmethane, hexanedioland formaldehyde. Polyacetals suitable for the invention may also beprepared by the polymerization of cyclic acetals.

The polycarbonates with hydroxyl groups used may be of the kind, e.g.,which may be prepared by reaction diols, e.g., propane-1,3-diol;butane-1, 4-diol; and/or hexane-1,6-diol or diethylene glycol,triethylene glycol or tetraethylene glycol, with diarylcarbonates, e.g.,diphenylcarbonates or phosgene.

The polyester amides and polyamides include, e.g., the predominantlylinear condensates obtained from polyvalent saturated and unsaturatedcarboxylic acids or their anhydrides, any polyvalent saturated andunsaturated amino alcohols, diamines, polyamines and mixtures thereof.

Polyhydroxyl compounds which contain urethane or urea groups, modifiedor unmodified natural polyols, e.g., castor oil, wood particles,cellulose, modified cellulose, carbohydrates and starches, may also beused. Additional products of alkylene oxides with phenol formaldehyderesins or with ureaformaldehyde resins are also suitable for the purposeof the invention.

Organic hydroxyl silicate compound as produced in U.S. Pat. No.4,139,549 may also be used in this invention to react with thepolyisocyanates.

Examples of these compounds which are to be used according to theinvention have been described in High Polymers, Volume XVI,"Polyurethanes, Chemistry and Technology", published by Saunders-FrischInterscience Publishers, New York, London, Volume I, 1962, pages 32 to42 and pages 44 to 54, and Volume II, 1964, pages 5 and 16 and pages 198and 199; and in Kunststoff-Handbuch, Volume III, Vieweg-Hochtlen,Carl-Hanser-Verlag, Munich 1966, on pages 45 to 71.

If the polyisocyanates or the prepolymer which contains NCO groups havea viscosity above 2000 cP at 25° C., it may be advantageous to reducethe viscosity thereof by mixing it with a low-viscosity organicpolyisocyanate and/or an inert blowing agent or solvent.

Inorganic polyisocyanates and isocyanate-terminated polyurethanesilicate prepolymers may also be used in this invention.

Polyisocyanate curing agents and/or polyisocyanate activators(catalysts) may be used in the process of producing polyurethaneresinous or foamed products. The following are examples ofpolyisocyanate curing agents and activators:

1. Water.

2. Water containing 10% to 70% by weight of an alkali metal silicate,such as sodium and/or potassium silicate. Crude commercial alkali metalsilicate may contain other substances, e.g., calcium silicate, magnesiumsilicate, borates or aluminates may also be used. The molar ratio ofalkali metal oxide to SiO₂ is not critical and may vary within the usuallimits, but is preferably between 4 to 1 and 0.2 to 1.

3. Water containing 20% to 50% by weight of ammonium silicate.

4. Water containing 5% to 40% by weight of magnesium oxide in the formof a colloidal dispersion.

5. Alkali metal metasilicate such as sodium metasilicate, potassiummetasilicate and commercial dry granular sodium and potassium silicates.Heating may be required to start the curing reaction.

6. Water containing 20% to 70% by weight of silica sol.

7. Activators (catalysts) which act as curing agents and are added tothe polyurethane or polyurethane prepolymer in the amount of 0.001% to10% by weight. They may be added in water.

(a) Tertiary amines, e.g., triethylamine; tributylamine;N-methyl-morpholine; N,N,N',N'-tetramethylenediamine;1,4-diazobicyclo-(2,2,2)-octane; N-methyl-N'-dimethylaminoethylpiperazine; N,N-dimethylbenzylamine; bis(N,N-diethylaminoethyl)-adepate;N,N-diethylbenzylamine; pentamethyldiethylenetriamine;N,N-dimethylcyclohexylamine; N,N,N',N'-tetramethyl-1,3-butanediamine;N,N-dimethyl-beta-phenylethylamine; and 1,2-dimethylimidazole. Suitabletertiary amine activators which contain hydrogen atoms which arereactive with isocyanate groups include, e.g., triethanolamine;triisopanolamine; N,N-dimethylethanolamine; N-methyldiethanolamine;N-ethyldiethanolamine; and their reactive products with alkylene oxides,e.g., propylene oxides and/or ethylene oxide and mixtures thereof.

(b) Organo-metallic compounds, preferably organo-tin compounds such astin salts of carboxylic acid, e.g., tin acetate, tin octoate, tin ethylhexoate, and tin laurate and the dialkyl tin salts of carboxylic acids,e.g., dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleateor diocyl tin diacetate.

(c) Silaamines with carbon-silicon bonds are described, e.g., in BritishPatent No. 1,090,589, may also be used as activators, e.g.,2,2,4-trimethyl-1,2-silamorpholine or1,3-diethylaminoethyl-tetramethyldisiloxane.

(d) Other examples of catalysts which may be used according to theinvention, and details of their action are described inKunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen,Carl-Hanser-Verlag, Munich, 1966, on pages 96 and 102.

8. Water containing 1% to 10% by weight of bases which contain nitrogensuch as tetraalkyl ammonium hydroxides.

9. Water containing 1% to 10% by weight of alkali metal hydroxides suchas sodium hydroxide; alkali metal phenolates such as sodium phenolate oralkali metal alcoholates such as sodium methylate.

10. Water containing sodium polysulfide in the amount of 1% to 10% byweight.

11. Water containing 20% to 70% by weight of a water-binding agent,being capable of absorbing water to form a solid or a gel, such ashydraulic cement, synthetic anhydrite, gypsum or burnt lime.

12. Mixtures of the above-named curing agents.

Surface-active additives (emulsifiers and foam stabilizers) may also beused according to the invention. Suitable emulsifiers are, e.g., thesodium salts of ricinoleic sulphonates or of fatty acid, or salts offatty acids with amines, e.g., oleic acid diethylamine or stearic aciddiethanolamine. Other surface-active additives are alkali metal orammonium salts of sulphonic acids, e.g., dodecylbenzine sulphonic acidor dinaphthyl methane disulphonic acid; or of fatty acids, e.g.,ricinoleic acid, or of polymeric fatty acids.

The foam stabilizers used are mainly water-soluble polyester siloxanes.These compounds generally have a polydimethylsiloxane group attached toa copolymer of ethylene oxide and propylene oxide. Foam stabilizers ofthis kind have been described in U.S. Pat. No. 3,629,308. Theseadditives are, preferably, used in quantities of up to 20%, based on thereaction mixture.

Negative catalyst, for example, substances which are acidic in reaction,e.g., hydrochloric acid or organic acid halides, known cell regulators,e.g., paraffins, fatty alcohols or dimethyl polysiloxanes, pigments ordyes, known flame-retarding agents, e.g., tris-chloroethylphosphate orammonium phosphate and polyphosphates, stabilizers against aging andweathering, plasticizers, fungicidal and bacteriocidal substances andfillers, e.g., barium sulphate, kieselguhr, carbon black or whiting, mayalso be used according to the invention.

Further examples of surface additives, foam stabilizers, cellregulators, negative catalysts, stabilizers, flame-retarding substances,plasticizers, dyes, fillers and fungicidal and bacteriocidal substancesand details about methods of using these additives and their action maybe found in Kunstsoff-Handbuch, Volume VI, published by Vieweg andHochtlen, Carl-Hanser-Verlag, Munich, 1966, on pages 103 to 113. Thehalogenated paraffins and inorganic salts of phosphoric acid are thepreferred fire-retarding agents.

Aqueous solutions of silicates may be prepared in the form of 25% to 70%silicates. Silica sols which may have an alkaline or acid pH may also beused; they should have solid contents of 15% to 50%. Silica sols aregenerally used in combination with aqueous silicate solutions. Thechoice of concentration depends mainly on the desired end product.Compact materials or materials with closed cells are, preferably,produced with concentrated silicated solutions which, if necessary, areadjusted to a lower viscosity by addition of alkali metal hydroxide.Solutions with concentrations of 40% to 70% by weight can be prepared inthis way. On the other hand, to produce open-celled, light-weight foams,it is preferred to use silicate solutions with concentrations of 25% to45% by weight in order to obtain lower viscosities, sufficiently longreaction times and low unit weights. Silicate solutions withconcentrations of 15% to 45% are also preferred when substantialquantities of finely divided inorganic fillers are used.

Suitable flame-resistant compounds may be used in the products of thisinvention such as those which contain halogen or phosphorus, e.g.,tributylphosphate, tris(2,3-dichloropropyl)-phosphate;polyoxypropylenechloromethylphosphonate; cresyldiphenylphosphate;tricresylphosphate; tris-(betachloroethyl)-phosphate;tris-(2,3-dichloropropyl)-phosphate; triphenylphosphate; ammoniumphosphate; perchlorinated diphenyl phosphate; perchlorinated terephenylphosphate; hexabromocyclodecane; tribromophenol; dibromopropyldiene;hexabromobenzene; octabromodiphenylether; pentabromotoluol;polytribromostyrol; tris-(bromocresyl)-phosphate; tetrabromobisphenol A;tetrabromphthalic acid anhydride; octabromodiphenyl phosphate;tri-(dibromopropyl)-phosphate; calcium hydrogen phosphate; sodium orpotassium dihydrogen phosphate; disodium or dipotassiumhydrogenphosphate; ammonium chloride, phosphoric acid; polyvinylchloridetetomers chloroparaffins as well as further phosphorus- and/orhalogen-containing flame-resistant compounds as they are described inKunststoff-Handbuch, Volume VII, Munich, 1966, pages 110 and 111, whichare incorporated herein by reference. The organic halogen-containingcomponents are, however, preferred in the polyurethane products.

The rations of the essential reactants and optional reactants which leadto the polyurethane resinous or foamed product of this invention mayvary, broadly speaking, with ranges as follows:

(a) 100 parts by weight of polyhydroxy lignin-cellulose polymerpolyester resinous product;

(b) 1 to 600 parts by weight of polyisocyanate, polyisothiocyanate orisocyanate-terminated polyurethane prepolymer;

(c) up to 20% by weight of a foam stabilizer;

(d) up to 50% by weight of a chemically inert blowing agent, boilingwithin the range of from <25° C. to 80° C.;

(e) up to 10% by weight of an activator;

(f) up to 200% by weight of a water-binding agent;

(g) up to 95% by weight of a polyol;

(h) up to 100% by weight of a curing agent;

(i) up to 5% by weight of an emulsifying agent.

Percentages are based on the weight of the reactants, polyhydroxylignin-cellulose polymer, polyol and polyisocyanate.

In the cases where the viscosity of the polyisocyanate is too high, itmay be reduced by adding a low-viscosity isocyanate, or even by addinginert solvents such as acetone, diethyl ether of diethylene glycol,ethyl acetate and the like.

In cases where the curing agent contains an aqueous alkali silicate, theisocyanate-terminated polyurethane prepolymer may be sulphonated. It isusually sufficient to react with isocyanate-terminated polyurethaneprepolymer with concentrated sulphuric acid or oleum of sulfur trioxidein order to produce a sulphonated poly(urethane silicate) prepolymercontaining sulphonic group in the amount 3 to 100 milli-equivalents/100g. The reaction will take place by thoroughly mixing the sulphuric acidor oleum or sulfur trioxide with the isocyanate-terminated polyurethaneprepolymer at ambient temperature and pressure. In some cases wheresulfur trioxide is used, an increased pressure is advantageous. Thepolyisocyanate may be modified to contain ionic groups before reactingwith the polyester resinous products.

The sulphonated isocyanate-terminated polyurethane prepolymer can bedirectly mixed with an aqueous silicate solution, in which case thecorresponding melt salt is formed in situ. The sulphonated polyurethaneprepolymer may be completely or partly neutralized at the onset by theaddition of amines, metal alcoholates, metal oxides, metal hydroxide ormetal carbonates.

Water-binding components may be used in this invention, includingorganic or inorganic water-binding substances which have, first, theability to chemically combine, preferably irreversibly, with water, andsecond, the ability to reinforce the poly(urethane silicate) plastics ofthe invention. The term "water-binding component" is used herein toidentify a material, preferably granular or particulate, which issufficiently anhydrous to be capable of absorbing water to form a solidor gel such as mortar of hydraulic cement.

A water-binding component such as hydraulic cement, syntheticanhydrides, gypsum or burnt lime may be added to any of the componentsto produce a tough, somewhat flexible solid or cellular solid concrete.The water-binding component may be added in amounts from 0 to 200% byweight, based on the weight of the reactants. When a water-binding agentis added and when the curing agent is an aqueous alkali metal silicatesolution, a halogen- or phosphorus-containing compound or mixturethereof may be added in the amount of 1% to 30% by weight, based on theweight of the reactants.

Suitable hydraulic cements are, in particular, Portland cement,quick-setting cement, blast-furnace Portland cement, mild-burnt cement,sulphate-resistant cement, brick cement, natural cement, lime cement,gypsum cement, pozzolan cement and calcium sulphate cement. In general,any mixture of fine ground lime, alumina and silica that will set to ahard product by admixture of water, which combines chemically with theother ingredients to form a hydrate, may be used. There are many kindsof cement which can be used in the production of the compositions of theinvention and they are so well known that a detailed description ofcement will not be given here; however, one can find such a detaileddescription in Encyclopedia of Chemical Technology, Volume 4, SecondEdition, published by Kirk-Othmer, pages 684 to 710, of the type ofcement which may be used in the production of this invention and whichare incorporated herein by reference.

Blowing agents may be used to improve or increase the foaming to producecellular solid plastics such as acetone, ethyl acetate, methanol,ethanol, halogenated alkanes, e.g., methylene chloride, chloroform,ethylidene chloride, vinylidene chloride, monofluorotrichloromethane,chlorofluoromethane, butane, hexane or diethyl ether. Compounds whichdecompose at temperatures above room temperature with liberation ofgases, e.g., nitrogen, such as azo compounds, azoisobutyric acidnitrile, may also act as blowing agents. Compressed air may act as ablowing agent. Other examples of blowing agents and details of the useof blowing agents are described in Kunststoff-Handbuch, Volume VII,published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich, 1966,e.g., on pages 108 and 109, 453 to 455 and 507 to 510.

The proportions of the components may be adjusted to a highly cellularsolid. When water is used, it reacts with the NCO group to produce CO₂and pores are produced in the product by the evolved CO₂. In certaincases, the CO₂ is rapidly evolved and escapes before the product hardensand a solid product can be produced, nearly completely free of aircells. When a high silicate content, from 80% to 99% by weight, isdesirable, such as when the final product is required to have mainly theproperties of an inorganic silicate plastic, in particular,high-temperature resistance and complete flame resistance, an alkalimetal silicate may be added with copolymer or polyol or be reacted withthe polyisocyanate to produce a polyurethane prepolymer. In that case,the function of the polyisocyanate is that of a non-volatile hardenerwhose reaction product is a high-molecular-weight polymer which reducesthe brittleness of the product.

When an alkali catalyst or alkali metal silicate is used in theinvention, fine metal powders, e.g., powdered calcium, magnesium,aluminum or zinc, may also act as the blowing agents by bringing aboutthe evolution of hydrogen. Compressed air may be mixed in the componentsand may also be used to mix the components, then be used as the blowingagent. These metal powders also have a hardening and reinforcing effect.

The properties of the foams (cellular solid) obtained from any givenformulation, e.g., their density in the moist state, depends to someextent on the details of the mixing process, e.g., the form and speed ofthe stirrer and the form of the mixing chamber, and also the selectedtemperature at which foaming is started. The foams will usually expand 3to 12 times their original volume.

The polyurethane silicate plastics produced by the invention have manyuses. The reaction mixture, with or without a blowing agent, may bemixed in a mixing apparatus; then the reaction mixture may be sprayed bymeans of compressed air or by the airless spraying process ontosurfaces; subsequently, the mixture expands and hardens in the form of acellular solid which is useful for insulation, filling, andmixture-proofing coating. The foaming material may also be forced,poured or injection-molded into cold or heated molds, which may berelief molds or solid or hollow molds, optionally by centrifugalcasting, and left to harden at room temperature or at temperatures up to200° C., at ambient pressure or at elevated pressure. In certain cases,it may be necessary to heat the mixing or spraying apparatus to initiatefoaming; then, once foaming has started, the heat evolved by thereaction between components continues the foaming until the reaction iscomplete. A temperature between 40° C. and 150° C. may be required inorder to initiate foaming. The blowing agent may be added to thepolyisocyanate polyhydroxy lignin-cellulose silicate polymer.

Reinforcing elements may quite easily be incorporated into the reactionmixtures. The inorganic and/or organic reinforcing elements may be,e.g., fibers, metal wires, foams, fabrics, fleeces or skeletons. Thereinforcing elements may be mixed with the reaction mixtures, forexample, by the fibrous web impregnation or by processes in which thereaction mixtures and reinforcing fibers are together applied to themold, for example, by means of a spray apparatus. The shaped productsobtainable in this way may be used as building elements, e.g., in theform of sandwich elements, either as such or after they have beenlaminated with metal, glass or plastics; if desired, these sandwichelements may be foamed. The products may be used as hollow bodies, e.g.,as containers for goods which may be required to be kept moist or cool,as filter materials or exchanges, as catalyst carriers or as carriers ofother active substances, as decorative elements, furniture componentsand fillings or for cavities. They may be used in the field of modelbuilding and mold building, and the production of molds for metalcasting may also be considered.

Instead of blowing agents, finely divided inorganic or organic hollowparticles, e.g., hollow expanded beads of glass, plastics and straw, maybe used for producing cellular solid products. These products may beused as insulating materials, cavity fillings, packaging materials,building materials which have good solvent resistance and advantageousfire-resistant characteristics. They may also be used as lightweightbuilding bricks in the form of sandwiches, e.g., with metal-coveringlayers for house building and the construction of motor vehicles andaircraft.

Organic or inorganic particles which are capable of foaming up or havealready been foamed may be incorporated in the fluid foaming reactionmixture, e.g., expanded clay, expanded glass, wood, cork, popcorn,hollow plastic beads such as beads of vinyl chloride polymers,polyethylene, styrene polymers, or foam particles of these polymers orother polymers, e.g., polysulphone, polyepoxide, polyurethane,poly(urethane silicate) copolymers, urea-formaldehyde,phenol-formaldehyde or polyimide polymers, or, alternatively, heaps ofthese particles may be permeated with foaming reaction mixtures toproduce insulation materials which have good fire-resistantcharacteristics.

The cellular solid products of the invention, in the aqueous or dry orimpregnated state, may subsequently be lacquered, metallized, coated,laminated, galvanized, vapor-treated, bonded or blocked. The cellularsolid products may be sawed, drilled, planed, polished, or other workingprocesses may be used to produce shaped products. The shaped products,with or without a filler, may be further modified in their properties bysubsequent heat treatment, oxidation processes, hot pressing, sinteringprocesses or surface melting or other compacting processes.

The novel cellular solid products of the invention are also suitable foruse as constructional materials due to their toughness and stiffness,yet they are still elastic. They are resistant to tension andcompression and have a high-dimensional stability to heat and high flameresistance. They have excellent sound-absorption capacity,heat-insulating capacity, fire resistance, and heat resistance whichmakes them useful for insulation. The cellular products of thisinvention may be foamed on the building site and, in many cases, used inplace of wood or hard fiber bonds. Any hollow forms may be used forfoaming. The brittle foams may be crushed and used as a filler, as asoil conditioner, as a substrate for the preparation of seedlings,cuttings and plants or cut flowers.

The foamed or solid concrete produced by reaction of the organicbroken-down lignin-cellulose polymer, polyol and polyisocyanate with awater-binding component may be used as surface coatings having goodadhesion and resistance-to-abrasion properties, as mortars, and formaking molded products, particularly in construction engineering andcivil engineering such as for building walls, igloos, boats and forroadbuilding, etc. These products are light-weight, thermal-insulatingmaterials with excellent mechanical properties and fire resistance. Theamount of water-binding component used varies greatly, depending on thetype of product desired, up to 200% by weight, based on weight ofreactants. In certain cases, it is desirable to add sand and gravel inthe amount of 1 to 6 parts by weight to each part by weight of thehydraulic cement. The mixture may be poured in place, troweled on orsprayed onto the desired surface to produce a solid or cellular solidproduct.

Fillers in the form of powders, granules, wire, fibers, dumb-bell shapedparticles, crystallites, spirals, rods, beads, hollow beads, foamparticles, non-woven webs, pieces of woven or knitted fabrics, tapes andpieces of foil of solid inorganic or organic substances, e.g., dolomite,chalk, alumina, asbestos, basic silicic acids, sand, talc, iron oxides,aluminum oxide and hydroxides, alkali metal silicates, zeolites, mixedsilicates, calcium silicate, calcium sulphates, aluminosilicates,cements, basalt wool or powder, glass fibers, carbon fibers, graphite,carbon black, Al-, Fe-, Cri- and Ag-powders, molybdenum sulphide, steelwool, bronze or copper meshes, silicon powder, expanded clay particles,hollow glass beads, glass powder, lava and pumice particles, wood chips,woodmeal, cork, cotton, straw, popcorn, coke or particles of filled orunfilled, foamed or unfoamed, stretched or unstretched organic polymers,may be added to the mixture of the Components in many applications.Among the numerous organic polymers which may be used, e.g., as powders,granules, foam particles, beads, hollow beads, foamable (butnot-yet-foamed) particles, fibers, tapes, woven fabrics, or fleeces, thefollowing may be mentioned as examples: Polystyrene, polyethylene,polypropylene, polyacrylonitrile, polybutadiene, polyisoprene,polytetrafluorethylene, aliphatic and aromatic polyesters, melamine,urea, phenol resins, phenol silicate resins, polyacetal resins, andfoils may be used for producing synthetic incombustible paper orfleeces.

When the polyhydroxy lignin-cellulose silicate polymer, produced by theprocess of this invention, and polyisocyanate are combined with expandedclay and an alkali metal silicate solution, a very good concrete isobtained which can, for example, be used as panels in the constructionfield. In this case, the foam material (expanded clay) plays the part ofthe binding material.

The polyhydroxy lignin-cellulose silicate polymer may be reacted with apolycarboxylic acid and/or a polycarboxylic acid anhydride to produce apolyester lignin-cellulose silicate resin.

The preferred method for producing lignin-cellulose resin is to mix 100parts by weight of the polyhydroxy lignin-cellulose silicate polymerwith 1 to 50 parts by weight of a polycarboxylic acid and/orpolycarboxylic acid anydride, then heat the mixture to just below theboiling temperature of the polycarboxylic acid and/or polycarboxylicacid anhydride while agitating, then gradually increasing thetemperature to 250° C. while agitating for from 30 minutes to 4 hours,thereby producing a polyester lignin-cellulose silicate resin.

The polycarboxylic acid and its anhydride may be aliphaticcycloaliphatic, aromatic and/or heterocyclic and may be substituted,e.g., with halogen atoms and may be unsaturated; examples include:Succinic acid, adipic acid, sebacic acid, suberic acid, azelaic acid,phthalic acid, phthalic acid anhydride, isophthalic acid,tetrahydrophthalic acid anhydride, trimetallic acid, hexahydrophthalicacid anhydride, tetrachlorophthalic acid anhydride, endomethylenetetrahydrophthalic acid anhydride, glutaric acid anhydride, fumaricacid, maleic acid and maleic acid anhydride and mixtures thereof.Dimeric and trimeric acid, fatty acid such as oleic acid, optionallymixed with monomeric fatty acids, dimethylterephthalate and bis-glycolterephthalate may also be used.

Long-chain unsaturated polyester resins may be made from dibasic acidsand dihydric alcohols. Either the dibasic acid or the dihydric alcoholmay be unsaturated. Usually a combination of unsaturated or saturateddibasic acids and dihydric alcohols is used to produce the unsaturatedpolyester resins. Instead of the dibasic acids, the correspondingpolycarboxylic acid ester of lower alcohols or their mixtures may beused for preparing the unsaturated polyester resins. An unsaturateddibasic acid such as maleic acid, maleic acid anhydride, fumaric acid,itaconic acid or mixtures thereof may be included in the production ofunsaturated polyester resins, except when an unsaturated alcohol isused.

A portion, up to 50% by weight, of the polycarboxylic acid and/orpolycarboxylic acid anhydride may be replaced by polymerable oils suchas unsaturated fatty acids (or their esters), tung oil, linseed oil,heated linseed oil, soybean oil, dehydrated castor oil, tall oil,cottonseed oil, sunflower oil, fish oil, perilla oil, safflower oil andmixtures thereof.

A portion, up to 50% by weight, of the polycarboxylic acid and/orpolycarboxylic acid anhydride may be replaced with a linear organiccarbonate selected from the group consisting of p-xylene glycolbis(ethyl carbonate), diethylene glycol bis(allyl carbonate) andmixtures thereof.

A portion, up to 50% by weight, of the substituted organic monohydroxycompound and polycarboxylic acid is replaced with an organic compoundcontaining hydroxyl and carboxylic radicals, selected from the groupconsisting of 10-hydroxy undecanoic acid, 2-hydroxy decanoic acid,ω-hydroxy pentadecanoic acid and mixtures thereof.

DESCRIPTION OF PREFERRED EMBODIMENTS

My invention will be illustrated in greater detail in the specificExamples which follow, which detail the preferred embodiments of myprocess. It should be understood that the scope of the invention is notlimited to the specific processes set out in the Examples. Parts andpercentages are by weight, unless otherwise indicated.

EXAMPLE 1

About 2 parts by weight of melted lye flakes (NaOH), 1 part by weight ofpolysilicic acid, and 2 parts by weight of fir sawdust are mixed, thenheated to between 150° C. and 220° C. while agitating at ambientpressure, with care being taken that the mixture does not burn, for 5 to60 minutes or until the mixture softens and expands into a dark-brown,thick liquid when hot. It cools to a solid, thereby producing abroken-down alkali metal plant silicate polymer which is water-soluble.

Other plant particles may be used in place of fir sawdust such as:

(a) oak sawdust;

(b) ash sawdust;

(c) seaweed;

(d) cotton;

(e) corn cobs;

(f) cotton stalks;

(g) bagasse;

(h) paper;

(i) oat straw;

(j) grass clippings;

(k) pine sawdust;

(l) equal parts of paper and fir sawdust.

EXAMPLE 2

About equal parts by weight of melted sodium hydroxide, sodiummetasilicate and a plant particle listed below are mixed at between 150°C. and 220° C. while agitating at ambient pressure for 5 to 60 minutesor until the mixture softens and expands into a thick brown liquid whichsolidifies on cooling, thereby producing a broken-down alkali metalplant silicate polymer. The polymer is ground into small particles.

(a) fir sawdust;

(b) oak sawdust;

(c) beech sawdust;

(d) redwood sawdust;

(e) gum sawdust;

(f) sycamore sawdust

(g) cotton stalk particles;

(h) mixture of weed particles;

(i) equal mixtures of (a) and newspapers;

(j) equal mixtures of (c) and cotton;

(k) pine sawdust;

(l) maple sawdust;

(m) elm sawdust;

(n) corn cob particles;

(o) seaweed particles;

(p) cornstalk particles;

(q) bagasse particles;

(r) mixtures thereof.

EXAMPLE 3

About equal parts by weight of potassium hydroxide, potassium silicateand a plant particle selected from the list below are mixed, then heatedto between 150° C. and 220° C. while agitating at ambient pressure for 5to 60 minutes or until the mixture softens and expands into adark-brown, thick liquid, thereby producing a broken-down alkali metalplant silicate polymer. The polymer is ground into small particles.

(a) fir sawdust;

(b) pine sawdust;

(c) seaweed particles;

(d) corn cob particles;

(e) corn stalk particles;

(f) ash sawdust;

(g) rice straw particles;

(h) wheat straw particles;

(i) bagasse particles;

(j) oak sawdust;

(k) gum sawdust;

(l) cedar sawdust.

EXAMPLE 4

About 4 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 2(b) and 4 parts by weight of propyleneoxide are mixed, then 6 N hydrochloric acid is slowly added until the pHis about 5 to 6 while agitating and keeping the temperature below theboiling point of propylene oxide; then the mixture is agitated from 30minutes to 2 hours, thereby producing a polyhydroxy lignin-cellulosesilicate polymer and sodium chloride.

EXAMPLE 5

About 100 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 3(a) are mixed with 50 parts by weight ofepichlorohydrin, then 6 N phosphoric acid is slowly added whileagitating and keeping the temperature below the boiling temperature ofepichlorohydrin until the pH is about 5 to 6. The mixture is thenagitated for between 30 minutes and 2 hours at ambient pressure, therebyproducing a polyhydroxy lignin-cellulose silicate polymer and sodiumphosphate.

EXAMPLE 6

About 100 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 2(b) are added to an autoclave; then 6 Nphosphoric acid is added until the pH is about 5 to 6; then 50 parts byweight of ethylene oxide are slowly added while agitating at 50 psi forfrom 30 minutes to 8 hours, thereby producing a polyhydroxylignin-cellulose silicate polymer.

Other Lewis acids may be used with the phosphoric acid, such as BF₃,acetic anhhydride, aluminum chloride, monochloro-acetic acid, phthalicacid, 4-chloro-2-hydroxy-benzoic acid, benzene sulphonic acid andstannic chloride.

EXAMPLE 7

About 100 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 1(l) are added to an autoclave, then 6 Nsulfuric acid is added while agitating until the pH is about 5 to 6;then 50 parts by weight of propylene oxide and 50 parts by weight ofethylene oxide are slowly added at 50 psi while agitating for from 30minutes to 8 hours; thereby producing a polyhydroxy lignin-cellulosesilicate polymer.

EXAMPLE 8

About 100 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 1(k), 100 parts by weight of propyleneoxide and 50 parts by weight of tetrahydrofuran are mixed, then 6 Nhydrochloric acid is slowly added while agitating and keeping thetemperature below the boiling temperature of propylene oxide until thepH is about 5 to 6. The mixture is agitated from 30 minutes to 8 hours,thereby producing a polyhydroxy lignin-cellulose silicate polymer andsodium chloride.

EXAMPLE 9

About 100 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 1(b), 300 parts by weight of propyleneoxide and 1 part by weight of BF₃ are mixed, then chloroacetic acid isslowly added while agitating and keeping the temperature below theboiling temperature of propylene oxide until the pH is about 5 to 6. Themixture is agitated at ambient pressure for 30 minutes to 8 hours,thereby producing a polyhydroxy lignin-cellulose silicate polymer andsalt. The salt and unreacted plant polymer are removed by decantationand filtration.

EXAMPLE 10

About 50 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 1(d), 50 parts by weight of thebroken-down alkali metal plant silicate polymer as produced in Example1(a), 100 parts by weight of styrene oxide, 100 parts by weight ofpropylene oxide and 50 parts by weight of trichlorobutylene oxide aremixed; then concentrated phosphoric acid is slowly added while agitatingand keeping the temperature below the boiling temperature of propyleneoxide until the pH is about 5 to 6. The mixture is agitated for from 30minutes to 8 hours, thereby producing a polyhydroxy lignin-cellulosesilicate polymer.

EXAMPLE 11

About equal parts by weight of tolylene diisocyanate and the polyhydroxylignin-cellulose silicate polymer as produced in Example 1 are mixed.The mixture slowly solidifies into a tough solid polyurethane silicateresin.

EXAMPLE 12

Example 11 is modified by adding about 10% trichlorotrifluoroethane, 1%by weight of sodium sulfosuccinate, 0.5% by weight of triethyldiamine,0.1% by weight of tin octoate and 1% by weight of a polymethylsiloxanesilicate, percentage based on the reaction mixture, thereby producing afoamed polyurethane silicate resin.

EXAMPLE 13

About 55 parts by weight of the polyhydroxy lignin-cellulose silicatepolymer as produced in Example 2, 0.5 part by weight of triethanolamine,0.1 part by weight of tin octate and 50 parts by weight of a compoundcontaining an isocyanate listed below are mixed and the mixture slowlysolidifies into a tough, solid polyurethane silicate resin.

    ______________________________________                                        Example                                                                              Polyisocyanate compound                                                ______________________________________                                        a      Polyphenylpolymethyleneisocyanate with an NCO                                 content of about 31%;                                                  b      2,6-toluene diisocyanate;                                              c      Methylene bis-phenyl diisocyanate;                                     d      Tolylene diisocyanate reacted with 5% propylene                               glycol;                                                                e      Crude toluene diisocyanate with an NCO content                                of about 18%;                                                          f      Equal parts by weight of crude toluene diisocyanate                           with an NCO content of about 18 and polyphenyl-                               polymethylene-isocyanates with an NCO content                                 of about 31;                                                           g      Methylene bis-phenyl diisocyanate reacted with a liquid                       polyepichlorohydrin to produce a prepolymer                                   containing about 16% NCO and 25% by weight of a                               resin extender, polyalphamethyl-styrene added;                         h      Naphthalene-15-diisocyanate;                                           i      Hexylene-1,6-diisocyanate.                                             ______________________________________                                    

EXAMPLE 14

Example 13 is modified wherein 10 parts by weight oftrichlorofluoromethane and 1 part by weight of a foam stabilizer(water-soluble polyester siloxane) are added with the triethanolamine,thereby producing a rigid foamed polyurethane silicate product.

EXAMPLE 15

About 5 parts by weight of the polyhydroxy lignin-cellulose silicatepolymer and 100 parts by weight of polyphenylpolymethyl-isocyanates withan NCO content of about 31 are thoroughly mixed and slowly reacted toproduce an isocyanate-terminated polyurethane silicate prepolymer.

EXAMPLE 16

The isocyanate-terminated polyurethane silicate prepolymer of Example 15is mixed with about 5% by weight of water and cured to produce a solidpolyurethane silicate product.

Other curing agents may be used in place of water such as aqueous sodiumsilicate, water containing silica sol, water containing 20% to 70% byweight of a water-binding agent, water containing 5% to 40% by weight ofa colloidal dispersion of magnesium oxide and mixtures thereof.

EXAMPLE 17

About 100 parts by weight of the isocyanate-terminated polyurethanesilicate prepolymer produced in Example 15, 1 part by weight oftriethylamine, 1 part by weight of a foam regulator (water-solublepolyester siloxane), 10 parts by weight of a polyethylene triol (mol.wt. 2,000) and 10 parts by weight of methylene chloride are thoroughlymixed and the mixture expands to produce a rigid foamed polyurethanesilicate product.

EXAMPLE 18

About 4 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 2(b), 2 parts by weight of an aqueoussolution containing 37% formaldehyde, 1 part by weight of phosphoricacid and 2 parts by weight of epichlorohydrin are added to an autoclave;then heated to a temperature just below the boiling point ofepichlorohydrin at 15 psi while agitating for 30 to 90 minutes, therebyproducing a polyhydroxy aldehyde lignin-cellulose silicate polymer andsodium phosphate.

Other aldehydes may be used in place of formaldehyde such asacetaldehyde, butyl aldehyde, chloral, acrolein, furfural, benzaldehyde,crotonaldehyde, propionaldehyde, pentanals, hexanals, octanals and theirsimple substitution products, semi-acetate and full acetals,paraformaldehyde and mixtures thereof. Compounds containing activealdehyde groups such as hexamethylene tetramine, phenoplasts andaminoplasts may also be used.

EXAMPLE 19

About 4 parts by weight of the broken-down alkali metal plant silicatepolymer is produced in Example 1(l), 1 part by weight of crotonaldehyde,2 parts by weight of epichlorohydrin, 1 part by weight of concentratedhydrochloric acid and 0.5 part by weight of propylene oxide are mixed,then heated to a temperature just below the boiling temperature ofepichlorohydrin or propylene oxide while agitating for 30 to 90 minutes,thereby producing polyhydroxy aldehyde lignin-cellulose silicate polymerand sodium chloride.

EXAMPLE 20

About 3 parts by weight of the broken-down alkali metal plant silicatepolymer as produced in Example 2(c), 1 part by weight of a liquidformaldehyde phenol resin produced in the presence of an acidic catalystand containing free aldehyde radicals, 1 part by weight of concentratedhydrochloric acid and 3 parts by weight of epichlorohydrin are mixed,then heated to just below the boiling temperature of epichlorohydrinwhile agitating for 30 to 90 minutes, thereby producing polyhydroxylignin-cellulose silicate polymer.

EXAMPLE 21

About 100 parts by weight of the polyhydroxy aldehyde lignin-cellulosesilicate polymer produced in Example 19 and 100 parts by weight of acompound containing at least two isocyanate groups listed below aremixed and reacted at ambient temperature and pressure, thereby producinga solid polyurethane product.

    ______________________________________                                        Example                                                                              Polyisocyanates                                                        ______________________________________                                        a      Tolylene diisocyanate;                                                 b      Polyphenylpolymethylene-isocyanates with an NCO                               content of about 31%;                                                  c      Naphthalene-1,5-diisocyanate;                                          d      Hexylene-1,6-diisocyanate;                                             e      Methylene bis-phenyl diisocyanate;                                     f      Crude toluene diisocyanate with an NCO content                                of about 18%;                                                          g      Tolylene diisocyanate reacted with 5% acetic acid;                     h      Polyphenylpolymethylene-isocyanates reacted with                              1% propylene glycol;                                                   i      Tolylene diisocyanate reacted with 10% silicic acid.                   ______________________________________                                    

EXAMPLE 22

Example 21 is modified by adding 15 parts by weight oftrichlorofluoromethane, 1 part by weight of triethylenediamine, 0.2 partby weight of tin acetate, and 1 part by weight of a foam regulator (awater-soluble polyester siloxane) with the polyhydroxy aldehydelignin-cellulose silicate polymer, thereby producing a rigid, foamedpolyisocyanate silicate product.

EXAMPLE 23

About 100 parts by weight of the polyhydroxy lignin-cellulose silicatepolymer produced in Example 4 and 50 parts by weight of phthalicanhydride are mixed, then heated to a temperature just below the boilingtemperature of phthalic anhydride while agitating at ambient pressurefor 30 minutes to 4 hours, thereby producing a polyesterlignin-cellulose silicate polymer.

EXAMPLE 24

About 100 parts by weight of the polyhydroxy lignin-cellulose silicatepolymer produced in Example 5, 25 parts by weight of phthalic anhydride,10 parts by weight of adipic acid and 25 parts by weight of maleicanhydride are mixed, then heated at ambient pressure to just below theboiling temperature of the reactants, then the temperature is graduallyincreased to 250° C. while agitating for 30 minutes to 4 hours, therebyproducing a solid polyester lignin-cellulose silicate polymer.

EXAMPLE 25

About 100 parts by weight of the polyhydroxy aldehyde lignin-cellulosesilicate polymer produced in Example 18, 25 parts by weight of phthalicanhydride, 10 parts by weight of linseed oil and 25 parts by weight ofsuccinic acid anhydride are mixed, then heated at ambient pressure tojust below the boiling temperature of the reactants, then thetemperature is gradually increased to about 250° C. while agitating for30 minutes to 4 hours, thereby producing a solid polyesterlignin-cellulose silicate polymer.

Other polymerizable oils may be used in place of linseed oil such assoybean oil, cottonseed oil, tung oil, fish oil, perilla oil, oiticicaoil, perilla oil, sunflower oil, safflower oil, walnut oil, dehydratedcastor oil, monoglyceride of vegetable oils and mixtures thereof.

Although specific conditions and ingredients have been described inconjunction with the above Examples of preferred embodiments, these maybe varied, and other reagents and additives may be used, where suitable,as described above, with similar results.

Other modifications and applications of this invention will occur tothose skilled in the art upon reading this disclosure. These areintended to be included within the scope of this invention, as definedin the appended claims.

I claim:
 1. The process for the production of polyurethane silicateproducts by the following steps:(a) mixing and reacting the followingcomponents, thereby producing a polyhydroxy lignin-cellulose silicatepolymer;(i) a broken-down alkali metal plant silicate polymer producedby heating a mixture of 3 parts by weight of a cellulose-containingplant and 1 to 2 parts by weight of an oxidated silicon compound with 2to 5 parts by weight of a melted alkali metal hydroxide to between 150°C. and 200° C. while agitating for 5 to 60 minutes; in an amount of 100parts by weight; (ii) an epoxide compound; in an amount of 1 to 3 partsby weight; (iii) a Lewis acid, in an amount wherein the pH of themixture of Components (i), (ii) and (iii) is 5 to 6; (b) mixing andreacting 100 parts by weight of the polyhydroxy lignin-cellulosesilicate polymer of step (a) and 1 to 600 parts by weight of a compoundcontaining at least 2 isocyanate groups, or polyisothiocyanate, therebyproducing a polyurethane silicate product.
 2. The product produced bythe process of claim
 1. 3. The process of claim 1, wherein the compoundcontaining at least 2 isocyanate groups is selected from the groupconsisting of arylene polyisocyanates, alkylene polyisocyanates,phosgenation products of aniline-formaldehyde condensation,isocyanate-terminated polyurethane prepolymers, and mixtures thereof. 4.The process of claim 1 wherein the compound containing at least 2isocyanate groups is a phosgenated product of aniline-formaldehydecondensation.
 5. The process of claim 1 wherein 1 to 100 parts by weightof an aldehyde are added to components (i), (ii) or (iii) of claim
 1. 6.The process of claim 5 wherein the aldehyde is selected from the groupconsisting of formaldehyde, acetaldehyde, propionic aldehyde, furfural,crotonaldehyde, acrolein, butyl aldehyde, paraformaldehyde, pentanals,hexanals, heptanals, and mixtures thereof.
 7. The product produced bythe process of claim
 5. 8. The process of claim 1 wherein up to 200% byweight of a water-binding agent, up to 100% by weight of a curing agentand an organic or inorganic filler, percentage based on the reactionmixture, are added in step (b) of claim
 1. 9. The product produced bythe process of claim
 8. 10. The process of claim 1 wherein up to 100% byweight of a curing agent, percentage based on the reaction mixture, isadded in step (b) of claim
 1. 11. The process of claim 1 wherein anorganic or inorganic filler is added in step (b) of claim
 1. 12. Theprocess of claim 1 wherein up to 10% by weight of an initiator,percentage based on the reaction mixture, is added in step (b) ofclaim
 1. 13. The process of claim 1 wherein the epoxide compound isselected from the group consisting of alkylene oxides, epihalohydrins,styrene oxide, tetrahydrofuran, and mixtures thereof.
 14. The process orclaim 1, wherein the Lewis acid is a meral acid selected from the groupconsisting of hydrochloric acid, sulfuric acid and phosphoric acid. 15.The process of claim 8 wherein the water-binding agent is selected fromthe group consisting of hydraulic cement, burnt lime, gypsum andsynthetic anhydrites.
 16. The process of claim 10 wherein the curingagent is selected from the group consisting of water, water containingsilica sol and an aqueous alkali metal silicate.
 17. The process ofclaim 12 wherein the initiator is selected from the group consisting oftertiary amines, organotin compounds, silaamines, and mixtures thereof.18. The process of claim 1 wherein up to 95 parts by weight of a polyolare added in step (b) of claim
 1. 19. The process of claim 1 wherein 100parts by weight of the polyhydroxy lignin-cellulose silicate polymer ofstep (a) of claim 26 are mixed and reacted with 1 to 50 parts by weightof a polycarboxylic acid, and up to 50 parts by weight of apolycarboxylic acid anhydride, thereby producing a polyester resin; thisis then added in step (b) of claim 1 in place of the polyhydroxylignin-cellulose silicate polymer.
 20. The product produced by theprocess of claim
 19. 21. The process of claim 19 wherein thepolycarboxylic acid is selected from the group consisting of aliphatic,cycloaliphatic, aromatic and heterocyclic polycarboxylic acids, andmixtures thereof.
 22. The process of claim 19 wherein the polycarboxylicacid anhydride is selected from the group consisting of phthalic acidanhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acidanhydride, tetrachlorophthalic acid anhydride, endomethylenetetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acidanhydride, and mixtures thereof.
 23. The product produced by the processof claim 17.